Solid state bipolar battery

ABSTRACT

A bipolar battery having a solid ionically conductive polymer material as its electrolyte enabling high voltage discharge.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.15/579,503 filed Dec. 4, 2017, which is a national stage entry ofInternational Patent Application No. PCT/US2016/036010 filed Jun. 6,2016, which claims priority to U.S. Provisional Patent Application No.62/170,959 filed Jun. 4, 2015. International Patent Application No.PCT/US2016/036010 is a continuation-in-part of U.S. patent applicationSer. No. 15/148,085 filed May 6, 2016 (now U.S. Pat. No. 11,251,455,issued Feb. 15, 2022), which claims priority to U.S. Provisional PatentApplication No. 62/158,841 filed May 8, 2015. International PatentApplication No. PCT/US2016/036010 is a continuation-in-part of U.S.patent application Ser. No. 14/676,173 filed Apr. 1, 2015 (now U.S. Pat.No. 11,145,857, issued Oct. 12, 2021), which claims priority to U.S.Provisional Patent Application No. 61/973,325 filed Apr. 1, 2014.International Patent Application No. PCT/US2016/036010 is acontinuation-in-part of U.S. patent application Ser. No. 14/559,430filed Dec. 3, 2014 (now U.S. Pat. No. 9,742,008, issued Aug. 22, 2017),which claims priority to U.S. Provisional Patent Application No.61/911,049 filed Dec. 3, 2013. International Patent Application No.PCT/US2016/036010 is a continuation-in-part of U.S. patent applicationSer. No. 13/861,170 filed Apr. 11, 2013 (now U.S. Pat. No. 9,819,053,issued Nov. 14, 2017), which claims priority to U.S. Provisional PatentApplication No. 61/622,705 filed Apr. 11, 2012. The entire contents ofeach of these applications is incorporated by reference herein.

FIELD OF THE INVENTION

One or more embodiments relate to bipolar electrodes including a solidionically conductive polymer material, manufacturing methods thereof,and bipolar batteries containing the same.

BACKGROUND OF THE INVENTION

U.S. Pat. No. 627,009 describes a lead acid battery constructed in sucha way that the “end electrodes and intermediate electrodes are connectedin electrical series . . . so that [the current collector] forms thesole conducting connection between the opposite sides of each of theintermediate electrodes.” Bipolar batteries have struggled to overcomethe challenge of isolating the liquid electrolyte to preventcommunication and short circuiting across cells.

Typical bipolar batteries have focused on using costly and complicatinginternal sealing mechanisms to contain liquid electrolytes to theirindividual cells. To avoid using sealing mechanisms, low conductivitysolid electrolytes and liquid gel electrolyte with seals have been triedin bipolar designs. However low ionic conductivity and high internalimpedance has limited the performance of such design.

The present embodiments overcome the above problems as well as provideadditional advantages.

SUMMARY OF THE INVENTION

According to an aspect, a bipolar battery including at least one bipolarelectrode, each having a positive electrode comprising a firstelectrochemically active material on one side of an electricallyconducting sheet and a negative electrode comprising a secondelectrochemically active material on the other side of the sheet; aplurality of electrolyte layers, each comprising a solid ionicallyconductive polymer material, both a terminal negative electrode andterminal positive electrode bounding the bipolar battery as the outsidelayers of the battery, wherein the terminal negative electrode islocated opposed to a positive electrode located on a first adjacentbipolar electrode with an electrolyte layer interposed therebetween,wherein the terminal positive electrode is located opposed to a negativeelectrode layer on a second bipolar electrode with an electrolyte layerinterposed therebetween; wherein the solid ionically conductive polymermaterial has a glassy state at room temperature, and comprises both atleast one cationic and anionic diffusing ion, wherein at least onediffusing ion is mobile in the glassy state.

In the aspect of the bipolar battery, each positive electrode and theadjacent anode comprise a sub-stack which also includes an interposedelectrolyte layer, wherein each sub-stack is separated from an adjacentsub-stack by an electrically conductive sheet, wherein each sub-stackhas a voltage.

Further aspects of the battery can include one or more of the following.

The bipolar battery, wherein the voltage of each sub-stack is equal toor less than 3 volts.

The bipolar battery, wherein the first electrochemically active materialcomprises zinc, aluminum, lithium or an intercalation material. Thebipolar battery, wherein the second electrochemically active materialcomprises manganese dioxide, sulfur or an intercalation material.

The bipolar battery further comprising a second sub-stack comprising asecond separator layer comprising solid ionically conductive polymerelectrolyte positioned between a second anode and second cathode layer,wherein said second sub-stack is positioned adjacent and in electricaland ionic communication with said first sub-stack and further comprisinga third current collector layer positioned adjacent second sub-stack andopposed from said first current collector layer.

The bipolar battery wherein each positive electrode comprises the solidionically conductive polymer material.

The bipolar battery wherein each negative electrode comprises the solidionically conductive polymer material.

The bipolar battery, wherein the voltage of the battery is greater than8 volts, and the distance between the terminal positive electrode andthe terminal negative electrode is less than six millimeters.

The bipolar battery wherein the electrolyte layer is extruded.

The bipolar battery wherein the positive electrode is extruded.

In the aspect, the battery the solid ionically conductive polymerelectrolyte further comprises: a crystallinity greater than 30%; amelting temperature; a glassy state; and wherein at least one diffusingion is mobile in the glassy state.

The battery wherein the solid ionically conductive polymer materialfurther comprises a plurality of charge transfer complexes. The batterywherein solid ionically conductive polymer material comprises aplurality of monomers, and wherein each charge transfer complex ispositioned on a monomer.

The battery wherein the electronic conductivity of the solid ionicallyconductive polymer material is less than 1×10″⁸ S/cm at roomtemperature.

The battery wherein the solid ionically conductive polymer materialcomprises: a plurality of monomers; a plurality of charge transfercomplexes, wherein each charge transfer complex is positioned on amonomer; wherein the electronic conductivity of the solid ionicallyconductive polymer electrolyte is less than 1×10″⁸/cm at roomtemperature.

The battery wherein the crystallinity of the solid ionically conductivepolymer material is greater than 30%.

The battery wherein the solid ionically conductive polymer material hasa glassy state which exists at temperatures below the meltingtemperature of the solid ionically conductive polymer material.

The battery wherein the solid ionically conductive polymer materialfurther comprises both a cationic and anionic diffusing ion, whereby atleast one diffusing ion is mobile in a glassy state of the solidionically conductive polymer electrolyte, and wherein the crystallinityof the solid ionically conductive polymer electrolyte is greater than30%.

The battery wherein the melting temperature of the solid ionicallyconductive polymer material is greater than 250° C.

The battery wherein the solid ionically conductive polymer material is athermoplastic.

The battery wherein the ionic conductivity of the solid ionicallyconductive polymer material is isotropic.

The battery wherein the solid ionically conductive polymer material isnon-flammable.

The battery wherein the Young's modulus of the solid ionicallyconductive polymer material is equal to or greater than 3.0 MPa.

The battery wherein the solid ionically conductive polymer material hasa glassy state, and at least one cationic and at least one anionicdiffusing ion, wherein each diffusing ion is mobile in the glassy state.

The battery wherein the ionic conductivity of the solid ionicallyconductive polymer material is greater than 1.0×10″⁵ S/cm at roomtemperature.

The battery wherein the solid ionically conductive polymer electrolytecomprises a single cationic diffusing ion, wherein the single anionicdiffusing ion comprises lithium, and wherein the diffusivity of thecationic diffusing ion is greater than 1.0×10¹² m²/s at roomtemperature. The battery wherein the solid ionically conductive polymermaterial comprises a single anionic diffusing ion, and wherein thediffusivity of the anionic diffusing ion is greater than 1.0×10″¹² m²/sat room temperature.

The battery wherein one of the at least cationic diffusing ion, has adiffusivity greater than 1.0×10″¹² m²/s.

The battery wherein one of the at least one anionic diffusing ion has adiffusivity greater than 1.0×10″¹² m²/s.

The battery wherein one of both the at least one anionic diffusing ionand at least one cationic diffusing ion has a diffusivity greater than1.0×10⁻¹² m²/s.

The battery wherein solid ionically conductive polymer material has anionic conductivity greater than 1×10″⁴ S/cm at room temperature.

The battery wherein the solid ionically conductive polymer material hasan ionic conductivity greater than 1×10″³ S/cm at 80° C.

The battery wherein the solid ionically conductive polymer material hasan ionic conductivity greater than 1×10″⁵ S/cm at −40° C.

The battery wherein the concentration of lithium is greater than 3 molesof lithium per liter of the solid ionically conductive polymer material.

The battery wherein each at least one cationic and anionic diffusing ionhave a diffusivity, wherein the cationic diffusivity is greater than theanionic diffusivity.

The battery wherein the cationic transference number of the solidionically conductive polymer material is greater than 0.5 and less than1.0.

The battery wherein at least one diffusing anion is monovalent.

The battery wherein at least one anionic diffusing ion compriseshydroxide, fluorine or boron.

The battery wherein the solid ionically conductive polymer materialcomprises a plurality of monomers and wherein there is at least oneanionic diffusing ion per monomer.

The battery wherein the solid ionically conductive polymer materialcomprises a plurality of monomers and wherein there is at least onecationic diffusing ion per monomer.

The battery wherein there is at least one mole of the lithium per literof solid ionically conductive polymer electrolyte.

The battery wherein the solid ionically conductive polymer materialcomprises a plurality of monomers, wherein each monomer comprises anaromatic or heterocyclic ring structure positioned in the backbone ofthe monomer. The battery wherein the solid ionically conductive polymermaterial further includes a heteroatom incorporated in the ringstructure or positioned on the backbone adjacent the ring structure.

The battery wherein the heteroatom is selected from the group consistingof sulfur, oxygen or nitrogen.

The battery wherein the heteroatom is positioned on the backbone of themonomer adjacent the ring structure.

The battery wherein the heteroatom is sulfur.

The battery wherein the solid ionically conductive polymer material ispi-conjugated.

The battery wherein the solid ionically conductive polymer materialcomprises a plurality of monomers, wherein the molecular weight of eachmonomer is greater than 100 grams/mole.

The battery wherein the charge transfer complex is formed by thereaction of a polymer, electron acceptor, and an ionic compound, whereineach cationic and anionic diffusing ion is a reaction product of theionic compound.

The battery wherein the solid ionically conductive polymer material isformed from at least one ionic compound, wherein the ionic compoundcomprises each at least one cationic and anionic diffusing ion.

The battery wherein the charge transfer complex is formed by thereaction of a polymer and an electron acceptor.

The battery wherein the solid ionically conductive polymer materialbecomes ionically conductive after being doped by an electron acceptorin the presence of an ionic compound that either contains both acationic and anionic diffusing ion or is convertible into both thecationic and anionic diffusing ion via reaction with the electronacceptor.

The battery wherein the solid ionically conductive polymer material isformed from the reaction product of a base polymer, electron acceptorand an ionic compound.

The battery wherein the base polymer is a conjugated polymer.

The battery wherein the base polymer is PPS or a liquid crystal polymer.

The battery wherein the electrolyte layer is formed into a film, whereinthe thickness of the film is between 200 and 15 micrometers.

The battery wherein the first electrochemically active materialcomprises an intercalation material. The battery wherein the firstelectrochemically active material comprises a lithium oxide comprisingnickel, cobalt or manganese, or a combination of two or all three ofthese elements.

The battery wherein the first electrochemically active material has anelectrochemical potential greater than 4.2 volts relative lithium metal.

The battery wherein the cathode has an electrode potential greater than4.2 volts relative lithium metal.

The battery wherein the first electrochemically active material isintermixed with an electrically conductive material and the solidionically conductive polymer electrolyte.

The battery wherein the electrically conductive material comprisescarbon.

The battery wherein the cathode comprises 70-90 percent by weight of thefirst electrochemically active material.

The battery wherein the cathode comprises 4-15 percent by weight of thesolid ionically conductive polymer material.

The battery wherein the cathode comprises 2-10 percent by weight of anelectrically conductive material.

The battery wherein the electrically conductive material comprisescarbon.

The battery wherein the cathode is formed from a slurry.

The battery wherein the cathode is positioned on a cathode collector.

The battery wherein the first electrochemically active materialcomprises a lithium oxide or a lithium phosphate that contain nickel,cobalt or manganese.

The battery wherein the first electrochemically active materialcomprises a lithium intercalation material, wherein the lithiumintercalation material comprises lithium.

The battery wherein the lithium intercalation material comprises LithiumNickel Cobalt Aluminum Oxide; Lithium Nickel Cobalt Manganese Oxide;Lithium Iron Phosphate; Lithium Manganese Oxide; Lithium cobaltphosphate or lithium manganese nickel oxide, Lithium Cobalt Oxide,LiTiS₂, LiNiO₂, or combinations thereof.

The battery wherein the first electrochemically active materialcomprises an electrochemically active cathode compound that reacts withlithium in a solid state redox reaction.

The battery wherein the electrochemically active cathode materialcomprises a metal halide; Sulfur; Selenium; Tellurium; Iodine; FeS₂ orLi₂S. The battery wherein the lithium intercalation material comprisesLithium Nickel Cobalt Manganese Oxide, wherein the atomic concentrationof nickel in the Lithium Nickel Cobalt Manganese Oxide is greater thanthe atomic concentration of cobalt or manganese.

The battery wherein the cathode is about 15 to 115 micrometers inthickness.

The battery wherein the cathode coating density in the range of 1.2 to3.6 g/cc.

The battery wherein the second electrochemically active materialcomprises an intercalation material.

The battery wherein the anode further comprises the solid ionicallyconductive polymer material, wherein the first electrochemically activematerial is mixed with the solid ionically conductive polymer material.

The battery wherein the second electrochemically active materialcomprises lithium metal.

The battery wherein the lithium metal in the anode 20 micrometers orless in thickness. The battery further comprising an anode currentcollector in ionic communication with the anode, wherein lithiumdeposits on a current collector when the battery is charged.

The battery wherein the density of the lithium deposited on the anode oranode side of the current collector is greater than 0.4 g/cc.

The battery wherein the second electrochemically active materialcomprises Silicon, Tin, antimony, lead, Cobalt, Iron, Titanium, Nickel,magnesium, aluminum, gallium, Germanium, phosphorus, arsenic, bismuth,zine, carbon and mixtures thereof.

The battery wherein the second electrochemically active materialcomprises an intercalation material, wherein the first electrochemicallyactive material comprises lithium metal.

The battery wherein a diffusing ion is cycled between the anode andcathode at a rate greater than 0.5 mA/cm² at room temperature.

The battery wherein a diffusing ion is cycled between the anode andcathode at a rate greater than 1.0 mA/cm² at room temperature.

The battery wherein a diffusing ion is cycled between the anode andcathode for greater than 150 cycles.

The battery wherein a diffusing ion is cycled between the anode andcathode at a rate greater than 3.0 mAh/cm² at room temperature forgreater than ten cycles.

The battery wherein a diffusing ion is cycled between the anode andcathode at a rate greater than 18.0 mAh/cm². The battery wherein adiffusing ion is cycled between the anode and cathode at a rate greaterthan 0.25 mAh/cm² at room temperature for greater than 150 cycles.

The battery wherein the cycling efficiency is greater than 99%.

The battery wherein the second electrolyte comprises the solid ionicallyconductive polymer electrolyte and is formed into a film, and attachedto a cathode.

The battery wherein an electrolyte layer is formed into a film, andattached to a anode. The bipolar battery wherein the charged voltage ofthe battery is greater than 8 volts. The bipolar battery of claim 1,wherein the charged voltage of the battery is greater than 12 volts.

The bipolar battery of claim 1, wherein the charged voltage of thebattery is greater than 20 volts.

The bipolar battery of claim 1, having a second cycle cycling efficiencygreater than 99%. The bipolar battery of claim 1, wherein the voltage ofthe battery is greater than 12 volts, and wherein the battery providesan amperage rate greater than 3 mA/cm².

In an aspect, a method of manufacturing a bipolar battery comprising thesteps of: mixing a polymer with an electron acceptor to create a firstmixture; heating the first mixture to form a reaction product comprisinga plurality charge transfer complexes; mixing at least one ioniccompound with the reaction product to form a solid ionically conductivepolymer material.

Further aspects of the method of manufacturing a battery can include oneor more of the following:

The method further comprising including mixing a first electrochemicallyactive material with the solid ionically conductive polymer material toform a cathode.

The method wherein the cathode forming step further includes mixing anelectrically conductive material with the first electrochemically activematerial and the solid ionically conductive polymer material.

The method wherein the cathode forming step further comprising acalendaring step wherein the density of the cathode is increased.

The method wherein the solid ionically conductive polymer material isformed into a film to form a solid ionically conductive polymerelectrolyte.

The method wherein the dopant is a quinone.

The method wherein the polymer is PPS, a conjugated polymer or a liquidcrystal polymer.

The method wherein the ionic compound is a salt, hydroxide, oxide orother material containing lithium.

The method wherein the ionic compound comprises lithium oxide, lithiumhydroxide, lithium nitrate, lithium bis-trifluoromethanesulfonimide,Lithium bis(fluorosulfonyl)imide, Lithium bis(oxalato)borate, lithiumtrifluoromethane sulfonate), lithium hexafluorophosphate, lithiumtetrafluoroborate, or lithium hexafluoroarsenate, and combinationsthereof.

The method wherein in the heating step the first mixture is heated to atemperature between 250 and 450 deg. C.

The method wherein the cathode is positioned adjacent a first side of aelectrically conducting bipolar current collector, and an anode ispositioned adjacent a second side of the bipolar current collector toform a bipolar electrode assembly.

The method wherein the solid ionically conductive polymer material isformed into a film to form two portions of solid ionically conductivepolymer electrolyte, and located on each side of a bipolar electrodeassembly.

The method further comprising an enclosure, and further comprising anassembly step wherein the bipolar electrode is positioned between thetwo current collectors and the to form a battery assembly, and thebattery assembly is placed within the enclosure.

The method in the bipolar electrode assembly step, the film is attachedto the anode, the cathode or both the anode and the cathode.

The method wherein in the attaching step the film is coextruded witheither the anode, cathode or both the anode and the cathode.

These and other features, advantages, and objects of the presentinvention will be further understood and appreciated by those skilled inthe art by reference to the following specification, claims, andappended drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

In the drawings:

FIG. 1 is a representation of a bipolar battery cross section;

FIG. 2A is a plot of a capacity-voltage (CV) charge curve of a bipolarbattery described in Example 5:

FIG. 2B is a plot of a capacity-voltage (CV) pulse discharge curve of abipolar battery described in Example 5;

FIG. 3 is cycle plot of a battery described in Example 6;

FIG. 4 is cycle plot of a battery described in Example 6;

FIG. 5 is open circuit voltammetry plot of a battery described inExample 7;

FIG. 6 is open circuit voltammetry plot of a battery described inExample 7;

FIG. 7 is an impedance plot of a battery described in Example 7.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

This application claims the benefit of U.S. Provisional PatentApplication No. 62/170,959 filed Jun. 4, 2015; hereby incorporated byreference; and also incorporates by reference U.S. Provisional PatentApplication No. 62/158,841 filed May 8, 2015, U.S. patent applicationSer. No. 14/559,430 filed Dec. 3, 2014; U.S. Provisional PatentApplication No. 61/911,049 filed Dec. 3, 2013; U.S. patent applicationSer. No. 13/861,170 filed Apr. 11, 2013; and U.S. Provisional PatentApplication No. 61/622,705 filed Apr. 11, 2012.

A bipolar battery is described which is enabled to operate efficientlyat a high voltage by a solid ionically conductive polymer material.

The following explanations of terms are provided to better detail thedescriptions of aspects, embodiments and objects that will be set forthin this section. Unless explained or defined otherwise, all technicaland scientific terms used herein have the same meaning as commonlyunderstood to one of ordinary skill in the art to which this disclosurebelongs. In order to facilitate review of the various embodiments of thedisclosure, the following explanations of specific terms are provided:

A depolarizer is a synonym of electrochemically active substance, i.e.,a substance which changes its oxidation state, or partakes in aformation or breaking of chemical bonds, in a charge-transfer step of anelectrochemical reaction and electrochemically active material.

Thermoplastic is a characteristic of a plastic material or polymer tobecome pliable or moldable above a specific temperature often around orat its melting temperature and to solidify upon cooling.

A “Solid” is characterized by the ability to keep its shape over anindefinitely long period, and is distinguished and different from amaterial in a liquid phase. The atomic structure of solids can be eithercrystalline or amorphous. Solids can be mixed with or be components incomposite structures. However, for purposes of this application and itsclaims, a solid material requires that that material be ionicallyconductive through the solid and not through any solvent, gel or liquidphase, unless it is otherwise described. For purposes of thisapplication and its claims, gelled (or wet) polymers and other materialsdependent on liquids for ionic conductivity are defined as not beingsolid electrolytes in that they rely on a liquid phase for their ionicconductivity. A polymer is typically organic and comprised of carbonbased macromolecules, each of which have one or more type of repeatingunits or monomers. Polymers are light-weight, ductile, usuallynon-conductive and melt at relatively low temperatures. Polymers can bemade into products by injection, blow and other molding processes,extrusion, pressing, stamping, three dimensional printing, machining andother plastic processes. Polymers typically have a glassy state attemperatures below the glass transition temperature Tg. This glasstemperature is a function of chain flexibility, and occurs when there isenough vibrational (thermal) energy in the system to create sufficientfree-volume to permit sequences of segments of the polymer macromoleculeto move together as a unit. However, in the glassy state of a polymer,there is typically no segmental motion of the polymer.

Polymers are distinguished from ceramics which are defined as inorganic,non-metallic materials; typically compounds consisting of metalscovalently bonded to oxygen, nitrogen or carbon, brittle, strong andnon-conducting.

The glass transition, which occurs in some polymers, is a midpointtemperature between the supercooled liquid state and a glassy state as apolymer material is cooled. The thermodynamic measurements of the glasstransition are done by measuring a physical property of the polymer,e.g. volume, enthalpy or entropy and other derivative properties as afunction of temperature. The glass transition temperature is observed onsuch a plot as a break in the selected property (volume of enthalpy) orfrom a change in slope (heat capacity or thermal expansion coefficient)at the transition temperature. Upon cooling a polymer from above the Tgto below the Tg, the polymer molecular mobility slows down until thepolymer reaches its glassy state.

As a polymer can comprise both amorphous and crystalline phase, polymercrystallinity is the amount of this crystalline phase relative theamount of the polymer and is represented as a percentage. Crystallinitypercentage can be calculated via x-ray diffraction of the polymer byanalysis of the relative areas of the amorphous and crystalline phases.

A polymer film is generally described as a thin portion of polymer, butshould be understood as equal to or less than 300 micrometers thick.

It is important to note that the ionic conductivity is different fromelectrical conductivity. Ionic conductivity depends on ionicdiffusivity, and the properties are related by the Nernst-Einsteinequation. Ionic conductivity and ionic diffusivity are both measures ofionic mobility. An ionic is mobile in a material if its diffusivity inthe material is positive (greater than zero), or it contributes to apositive conductivity. All such ionic mobility measurements are taken atroom temperature (around 21° C.), unless otherwise stated. As ionicmobility is affected by temperature, it can be difficult to detect atlow temperatures. Equipment detection limits can be a factor indetermining small mobility amounts. Mobility can be understood asdiffusivity of an ion at least 1×10″¹⁴ m²/s and preferably at least1×10″¹³ m²/s, which both communicate an ion is mobile in a material.

A solid polymer ionically conducting material is a solid that comprisesa polymer and that conducts ions as will be further described.

An aspect includes a method of synthesizing a solid ionically conductivepolymer material from at least three distinct components: a polymer, adopant and an ionic compound.

The components and method of synthesis are chosen for the particularapplication of the material. The selection of the polymer, dopant andionic compound may also vary based on the desired performance of thematerial. For example, the desired components and method of synthesismay be determined by optimization of a desired physical characteristic(e.g. ionic conductivity). Synthesis:

The method of synthesis can also vary depending on the particularcomponents and the desired form of the end material (e.g. film,particulate, etc.). However, the method includes the basic steps ofmixing at least two of the components initially, adding the thirdcomponent in an optional second mixing step, and heating thecomponents/reactants to synthesis the solid ionically conducting polymermaterial in a heating step. In one aspect of the invention, theresulting mixture can be optionally formed into a film of desired size.If the dopant was not present in the mixture produced in the first step,then it can be subsequently added to the mixture while heat andoptionally pressure (positive pressure or vacuum) are applied. All threecomponents can be present and mixed and heated to complete the synthesisof the solid ionically conductive polymer material in a single step.However, this heating step can be done when in a separate step from anymixing or can completed while mixing is being done. The heating step canbe performed regardless of the form of the mixture (e.g. film,particulate, etc.) In an aspect of the synthesis method, all threecomponents are mixed and then extruded into a film. The film is heatedto complete the synthesis.

When the solid ionically conducting polymer material is synthesized, acolor change occurs which can be visually observed as the reactantscolor is a relatively light color, and the solid ionically conductingpolymer material is a relatively dark or black color it is believed thatthis color change occurs as charge transfer complexes are being formed,and can occur gradually or quickly depending on the synthesis method. Anaspect of the method of synthesis is mixing the base polymer, ioniccompound and dopant together and heating the mixture in a second step.As the dopant can be in the gas phase, the heating step can be performedin the presence of the dopant. The mixing step can be performed in anextruder, blender, mill or other equipment typical of plasticprocessing. The heating step can last several hours (e.g. twenty-four(24) hours) and the color change is a reliable indication that synthesisis complete or partially complete. Additional heating past synthesis(color change) does not appear to negatively affect the material.

In an aspect of the synthesis method, the base polymer and ioniccompound can be first mixed. The dopant is then mixed with thepolymer-ionic compound mixture and heated. The heating can be applied tothe mixture during the second mixture step or subsequent to the mixingstep.

In another aspect of the synthesis method, the base polymer and thedopant are first mixed, and then heated. This heating step can beapplied after the mixing or during, and produces a color changeindicating the formation of the charge transfer complexes and thereaction between the dopant and the base polymer. The ionic compound isthen mixed to the reacted polymer dopant material to complete theformation of the solid ionically conducting polymer material.

Typical methods of adding the dopant are known to those skilled in theart and can include vapor doping of film containing the base polymer andionic compound and other doping methods known to those skilled in theart Upon doping the solid polymer material becomes ionically conductive,and it is believed that he doping acts to activate the ionic componentsof the solid polymer material so they are diffusing ions.

Other non-reactive components can be added to the above describedmixtures during the initial mixing steps, secondary mixing steps ormixing steps subsequent to heating. Such other components include butare not limited to depolarizers or electrochemically active materialssuch as anode or cathode active materials, electrically conductivematerials such as carbons, rheological agents such as binders orextrusion aids (e.g. ethylene propylene diene monomer “EPDM”), catalystsand other components useful to achieve the desired physical propertiesof the mixture.

Polymers that are useful as reactants in the synthesis of the solidionically conductive polymer material are electron donors or polymerswhich can be oxidized by electron acceptors. Semi-crystalline polymerswith a crystallinity index greater than 30%, and greater than 50% aresuitable reactant polymers. Totally crystalline polymer materials suchas liquid crystal polymers (“LCPs”) are also useful as reactantpolymers. LCPs are totally crystalline and therefore their crystallinityindex is hereby defined as 100%. Undoped conjugated polymers andpolymers such as polyphenylene sulfide (“PPS”) are also suitable polymerreactants.

Polymers are typically not electrically conductive. For example, virginPPS has electrical conductivity of 10″²⁰ S cm″¹. Non-electricallyconductive polymers are suitable reactant polymers.

In an aspect, polymers useful as reactants can possess an aromatic orheterocyclic component in the backbone of each repeating monomer group,and a heteroatom either incorporated in the heterocyclic ring orpositioned along the backbone in a position adjacent the aromatic ring.The heteroatom can be located directly on the backbone or bonded to acarbon atom which is positioned directly on the backbone. In both caseswhere the heteroatom is located on the backbone or bonded to a carbonatom positioned on the backbone, the backbone atom is positioned on thebackbone adjacent to an aromatic ring. Non-limiting examples of thepolymers used in this aspect of the invention can be selected from thegroup including PPS, Poly(p-phenylene oxide)(“PPO”), LCPs, Polyetherether ketone (“PEEK”), Polyphthalamide (“PPA”), Polypyrrole,Polyaniline, and Polysulfone. Copolymers including monomers of thelisted polymers and mixtures of these polymers may also be used. Forexample, copolymers of p-hydroxybenzoic acid can be appropriate liquidcrystal polymer base polymers.

Table 1 details non-limiting examples of reactant polymers useful in thesynthesis of the solid ionically conductive polymer material along withmonomer structure and some physical property information which should beconsidered also non-limiting as polymers can take multiple forms whichcan affect their physical properties.

TABLE 1 Melting Pt. Polymer Monomer Structure (C) MW PPS polyphenylenesulfide

285 109 PPO Poly(p- phenylene oxide)

262 92 PEEK Polyether ether ketone

335 288 PPA Polyphthalamide

312 Polypyrrole

Polyaniline Poly- Phenylamine [C₆H₄NH]_(n)

385 442 Polysulfone

240 Xydar (LCP)

Vectran Poly- paraphenylene [—CO—C₆H₄—CO— NH—C₆H₄—NH—]_(n)

Polyvinylidene fluoride (PVDF)

177 Polyacrylonitrile (PAN)

300 Polytetrafluoro- ethylene (PTFE)

327 Polyethylene (PE)

115-135

Dopants that are useful as reactants in the synthesis of the solidionically conductive polymer material are electron acceptors oroxidants. It is believed that the dopant acts to release ions for ionictransport and mobility, and it is believed to create a site analogous toa charge transfer complex or site within the polymer to allow for ionicconductivity. Non-limiting examples of useful dopants are quinones suchas: 2,3-dicyano-5,6-dichlorodicyanoquinone (C₈Cl₂N₂O₂) also known as“DDQ”, and tetrachloro-1,4-benzoquinone (C₆Cl₄O₂), also known aschloranil, tetracyanoethylene (C₆N₄) also known as TCNE, sulfur trioxide (“SO₃”), ozone (tri oxygen or O3), oxygen (O₂, including air),transition metal oxides including manganese dioxide (“MnO₂”), or anysuitable electron acceptor, etc. and combinations thereof. Dopants thatare temperature stable at the temperatures of the synthesis heating stepare useful, and quinones and other dopants which are both temperaturestable and strong oxidizers quinones are very useful. Table 2 provides anon-limiting listing of dopants, along with their chemical diagrams.

TABLE 2 Dopant Formula Structure 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) C₆Cl₂(CN)₂O₂

Tetrachloro-1,4-benzoquinone (chloranil) C₆Cl₄O₂

Tetracyanoethylene (TCNE) C₆N₄

Sulfur Trioxide SO₃ Ozone O₃ Oxygen O₂ Transition Metal OxidesM_(x)O_(y) (M = Transition Metal, x and y are equal to or greater than1)

Ionic compounds that are useful as reactants in the synthesis of thesolid ionically conductive polymer material are compounds that releasedesired ions during the synthesis of the solid ionically conductivepolymer material. The ionic compound is distinct from the dopant in thatboth an ionic compound and a dopant are required. The particular ioniccompound included in the synthesis depends on the utility desired forthe material. For example, in an aspect where it would be desired tohave a lithium cation which is ionically mobile in the solid ionicallyconductive polymer material, a lithium hydroxide, or a lithium oxideconvertible to a lithium and hydroxide ion would be appropriate. Aswould be any lithium containing compound that releases both a lithiumcathode and a diffusing anion during synthesis. A non-limiting group ofsuch lithium ionic compounds includes those used as lithium salts inorganic solvents. Non-limiting examples include Li₂O, UiH, LiNO₃, LiTFSI(lithium bis-trifluoromnethanesulfonimide), LiFSI (Lithiumbis(fluorosulfonyl)imide), Lithium bis(oxalato)borate (LiB(C₂O₄)₂“LiBOB”), lithium triflate LiCF₃O₃S (lithium trifluoromethanesulfonate), LiPF6 (lithium hexafluorophosphate), LiBF4 (lithiumtetrafluoroborate), LiAsF6 (lithium hexafluoroarsenate) and otherlithium salts and combinations thereof. Hydrated forms (e.g.monohydride) of these compounds can be used to simplify handling of thecompounds. Inorganic oxides, chlorides and hydroxide are suitable ioniccompounds in that they dissociate during synthesis to create at leastone anionic and cationic diffusing ion. Any such ionic compound thatdissociates to create at least one anionic and cationic diffusing ionwould similarly be suitable. Multiple ionic compounds can also be usefulthat result in multiple anionic and cationic diffusing ions can bepreferred.

The purity of the materials is potentially important so as to preventany unintended side reactions and to maximize the effectiveness of thesynthesis reaction to produce a highly conductive material.Substantially pure reactants with generally high purities of the dopant,base polymer and the ionic compound are useful, and purities greaterthan 98% are more useful with even higher purities, e.g. LiOH: 99.6%,DDQ: >98%, and Chloranil: >99% also useful.

To further describe the utility of the solid ionically conductivepolymer material and the versatility of the above described method ofthe synthesis of the solid ionically conductive polymer material, use ofthe solid ionically conductive polymer material in certain aspects ofbipolar electrochemical applications are described:

The technical benefits of bipolar battery design cross several areas,including flexibility in the overall voltage provided by the battery,increased energy density, decreased internal impedance, and in the caseof the Ionic bipolar battery—a high voltage cell with very high safety.The voltage flexibility enabled by the bipolar design is important tothe market application of the cell, where desirable voltage windows(such as 4 V lithium ion, 12 V for automotive, etc.) can be matched, andis discussed below. However, a strong benefit also exists in theflexibility that this design gives to considering electrode coupleswhich would normally be discounted because of lower voltage. The lowervoltage of these electrode couples can be offset by the bipolar design,stacking bipolar cell units and creating a higher overall cell voltage.The potential benefits of utilizing lower voltage electrode materialscan include low cost, high capacity, improved stability and cycle life,inherent safety and environmentally benign material properties. Thus,the bipolar battery design not only yields greater battery voltageflexibility, but also opens a much greater array of material choices toimprove manufacturing.

Another aspect of the bipolar battery is the combination of a highvoltage system with a fundamentally safe battery chemistry. Safetytesting of the bipolar battery has demonstrated low temperatures duringdirect short circuits and abusive puncture tests. This shows that highvoltage batteries, which can be used in place of traditional liquidlithium ion batteries, can also be very safe and benign toward abusiveconditions. This provides a significant benefit to the end user of thebattery.

The benefits of bipolar battery construction—increased energy, decreasedimpedance, improved safety, and voltage flexibility—provide directadvantages over existing battery solutions in a range of marketapplications. Voltage flexibility may be one of the most important ofthese advantages Currently, battery chemistry selection and designchoices of the end application are interlinked decisions—the voltage ofthe chemistry affects the end application's design, and theapplication's voltage requirements narrow the list of potentialchemistry choices. Many consumer electronics, for example, are designedto run on 4 volt lithium ion batteries, making less expensive and lowervoltage chemistries such as alkaline and nickel metal hydride anundesirable fit. Electric vehicles, on the other hand, are designed torun on very high voltage systems, necessitating complicated and bulkybattery packs with multiple modules in series to increase the voltage.

Bipolar batteries provide much more voltage flexibility than existingsolutions. By allowing low voltage chemistries to compete with moreexpensive lithium ion technologies and by minimizing packaging in highvoltage batteries for electric vehicle and other applications, bipolarbatteries have cost and performance advantages over existingtechnologies. A four-layer bipolar nickel metal hydride batterycontaining the solid ionically conductive polymer material, for example,is 4.8 volts and could be used in consumer electronics applicationswhere battery cost is a driver. Furthermore, for high voltageapplications, a ten-layer lithium ion battery with solid ionicallyconductive polymer material has an electric potential of nearly 40 voltswith significantly less packaging than ten four-volt lithium ion cellsconnected in series.

Bipolar batteries seek to internally connect multiple electrochemicalcells in series. In this configuration, the cathode of the first cellshares a current collector with the anode of the next cell to create aseries connection. Electrons flow directly through this currentcollector from the anode to the cathode. At the last anode in theseries, electrons flow out into the battery's end current collector,which is connected to an external terminal. This configuration resultsin a battery with a total voltage that is the sum of the individual cellvoltages, enabling much more voltage flexibility than with traditionalcell layouts. FIG. 1 shows this configuration for a three-cell bipolarbattery.

Referring to FIG. 1 , there is shown a pictorial representation of abipolar battery cross section. The bipolar battery 10 includes aplurality of both bipolar electrodes and anode-cathode couples orsub-stack assemblies, with the latter being labeled by V1, V2 and V3 forthe sub-voltages these couples provide. Each bipolar electrode comprisesa bipolar current collector 20 a and 20 b. Adjacent each bipolar currentcollector is both an anode 30 a and 30 b, and a cathode 40 a and 40 b.The bipolar electrodes are separated from each other by a layer of thesolid ionically conductive polymer material electrolyte 50 a. Terminalelectrodes: anode 30 d, and cathode 40 c are located in coupledopposition to the cathode 40 b and anode 30 a respectively and separatedby the interposed electrolyte comprising the solid ionically conductivepolymer electrolyte 50 b and 50 c respectively. As each terminalelectrode is positioned at a battery end, an end current collector 60 aand 60 b are located in electrical connection with each terminalelectrode. The end current collectors can act a battery terminals or inan aspect can be in electrical connection with battery terminals. Thebattery terminals can be connected to either an open circuit or a loadwherein the battery will provide either an open circuit voltage e- or anelectron flow to the load.

The bipolar battery includes at least one bipolar electrode, and in FIG.1 there is shown two bipolar electrodes positioned adjacent each otherin an aspect where there is a plurality of bipolar electrodes, eachwould be similarly positioned with a layer of electrolyte therebetween.Each bipolar electrode including a positive electrode having a firstelectrochemically active material on one side of an electricallyconducting sheet and a negative electrode having a secondelectrochemically active material on the other side of the sheet.

The number of electrolyte layers, each comprising a solid ionicallyconductive polymer material depends on the number of bipolar electrodes,and a plurality plus one of electrolyte layers would be required toaccommodate a plurality of bipolar electrodes. Each electrolyte layer,containing the solid ionically conductive polymer material enablessignificant ionic conductivity at room temperature which enables thebipolar battery to both be a stable system and to perform at high drainrates.

Each terminal electrode, i.e. terminal negative electrode (anode) 30 dand the terminal positive electrode (cathode) 40 c, is not a componentof a bipolar electrode but form a sub stack with an opposed electrodethat is a bipolar electrode component. The terminal negative electrodeis located opposed to and in electrochemically coupled relation to apositive electrode located on a first adjacent bipolar electrode with anelectrolyte layer interposed therebetween. Similarly, the terminalpositive electrode is located opposed to a negative electrode layer on asecond adjacent bipolar electrode with an electrolyte layer interposedtherebetween.

In the bipolar battery 10, each positive electrode 40 a, 40 b, 40 c andthe adjacent anode 30 a, 30 b, 30 d comprise a sub-stack which alsoincludes an electrolyte layer. For example, components 40 b, 50 b and 30d comprise a first sub-stack which generates a voltage V3. Eachsub-stack is separated from an adjacent sub-stack by an electricallyconductive sheet, which conducts the electrons from each sub-stack in aseries to produce an aggregate battery voltage, as it is in electricalcommunication with each sub-stack in the battery.

The sub-stack comprising the electrolyte layer 50 a positioned betweenanode 30 b and cathode 40 a, and generates voltage V2. The secondsub-stack is positioned adjacent and in electrical but not ioniccommunication with the first sub-stack via the bipolar current collector20 b, and also in electrical connection with a third sub-stack viabipolar current collector 20 a which is positioned adjacent the secondsub-stack and bounds the second sub-stack on one end with the bipolarcurrent collector 20 b positioned opposed from current collector layer20 a and bounding the opposite end.

The voltage of each sub-stack depends on the relative electropotentialof the included electrodes. The sub-stack voltage can be is equal to orless than 3 volts or be very high e.g. greater than 4.2 volts, orgreater than 5 volts. The electropotential of the electrodes depends onthe electropotential of the included electrochemically active materials.Anode electrodes can include zinc, aluminum, lithium, an intercalationmaterial and many other electrochemically active materials. Cathodeelectrodes can include manganese dioxide, sulfur, an intercalation andmany other electrochemically active materials.

The bipolar current collectors 20 a and 20 b are used for both thecathode 40 a and 40 b and anode 30 a and 30 b of adjacent bipolar cellunits. The bipolar battery 10 uses one less current collector for eachelectrochemical pair, which reduces the volume and weight occupied byinactive components. Depending on the number of bipolar cell units inthe battery, which can be considerable in large high-voltage batteries,the number of current collectors eliminated from the design can besubstantial. Furthermore, since the bipolar current collector transferselectrons directly between the cathode and anode, across the entire faceof the electrodes, the thickness of the current collector can be verythin, even for the highest rate cell designs. Thus, significantincreases in volumetric and gravimetric energy densities result from thebipolar cell construction, where less current collectors are needed, andthin current collectors can be utilized. The true energy densityimprovement will depend on the specific design used in the system, butit is estimated that the reduction in the number of current collectorsalone can increase the energy density by 10 to 15%. The utilization ofthin current collectors in a high rate design, along with theelimination in external cell packaging (battery case and terminals) formultiple cells connected in series is estimated to provide another 10 to25% increase in energy density, depending again on the size and voltageof the bipolar cell in question.

Bipolar batteries are especially useful for high rate applications,because the bipolar design provides lower internal impedance compared toa traditional battery design. This lower internal impedance results in abattery which is able to be charged and discharged at a faster rate, andprovide higher currents for demanding high power applications. Thereason that the bipolar battery has inherently lower impedance is due todirect current flow across the entire face of the electrodes betweenbipolar cell units. In a traditional cell, current flows along theelectrode from the electrode tab, down to the furthest point. In abipolar cell, the current can directly transfer between the cathode andanode throughout the entire area of the bipolar current collector,travelling a distance of microns rather than tens of centimeters, whichcorresponds to the thickness of the bipolar current collector. Thisprovides a significant benefit in lowering the impedance and DCresistance (Rdc) of the cell, and results in the cell providing a highervoltage when placed under load. The bipolar current collector 20 a and20 b can be copper, aluminum, stainless steel or any highly electricallyconductive material that is thin and shaped to be positioned between theanode and cathodes.

The end current collectors 60 a and 60 b can be the same material or anidentical component as the bipolar current collectors. In an aspect theend current collectors can be electrically conducting tabs which areaffixed to the end electrodes to conduct current in and out of thebattery from the respective terminals Unlike the bipolar currentcollectors, which extend across the entire adjacent surface of theirelectrodes, the end current collectors need not act to prevent theproximity of the bipolar electrode anodes and cathode as there is noelectrode couple.

Each anode 30 a, 30 b and 30 d can comprise an electrochemically activematerial appropriate for the desired electrochemical system. Theanode-cathode couple is not restrictive as the bipolar battery 10 cancomprise any electrochemical couple which includes solid materials asthe electrochemically active couple (anode and cathode). Althoughlithium batteries are described, lithium batteries are an aspect and notthe sole electrochemical system. In the aspect where the electrochemicalcouple comprises lithium as the electrochemically active material of theanode, the anode can comprise lithium metal in an aspect, or a lithiumintercalation material in another aspect.

In the aspect when an anode intercalation material is used as the anodeelectrochemically active material, useful anode materials includetypical anode intercalation materials comprising: lithium titanium oxide(LTO), Silicon (Si), germanium (Ge), and tin (Sn) anodes doped andundoped; and other elements, such as antimony (Sb), lead (Pb), Cobalt(Co), Iron (Fe), Titanium (Ti), Nickel (Ni), magnesium (Mg), aluminum(Al), gallium (Ga), Germanium (Ge), phosphorus (P), arsenic (As),bismuth (Bi), and zinc (Zn) doped and undoped; oxides, nitrides,phosphides, and hydrides of the foregoing; and carbons (C) includingnanostructured carbon, graphite, graphene and other materials includingcarbon, and mixtures thereof in this aspect the anode intercalationmaterial can be mixed with and dispersed within the solid ionicallyconducting polymer material such that the solid ionically conductingpolymer material can act to ionically conduct the lithium ions to andfrom the intercalation material during both intercalation anddeintercalation (or lithiation/delithiation). Electrically conductiveadditives can be additionally added to such an intercalation anode toenable electrons from flow from the electrochemically active material tothe adjacent current collector.

In the aspect when lithium metal is used, the lithium can be added withthe cathode material, added to the anode as lithium foil, dispersed inthe solid ionically conducting polymer material, or added to bothbattery components. The solid ionically conductive polymer electrolyteacts to transport the lithium metal to and from the anode and thereforemust be positioned within the battery so it is enabled to do so. Thusthe solid ionically conductive polymer electrolyte can be positioned asa film layer, or any other shape which enables the solid ionicallyconductive polymer electrolyte to perform its lithium ion conduction.The thickness of the solid ionically conductive polymer electrolyte canbe in a desired range of uniform thicknesses such as 200 to 25micrometers or thinner. To aid in extrusion of the solid ionicallyconductive polymer electrolyte, a rheological or extrusion aid can beadded such as EPDM (ethylene propylene diene monomer) in amountsnecessary to affect the desired extrusion properties.

Each cathode 40 a, 40 b and 40 c can comprise an electrochemicallyactive material appropriate for the desired electrochemical system andthe anode-cathode couple as the bipolar battery 10 can comprise anyelectrochemical couple which includes solid materials as theelectrochemically active couple (anode and cathode). Although lithiumbatteries are described, lithium batteries are an aspect and not thesole electrochemical system. Typical electrochemically active cathodecompounds which can be used include but are not limited to: NCA—LithiumNickel Cobalt Aluminum Oxide (LiNiCoAlO₂), NCM (NMC)—Lithium NickelCobalt Manganese Oxide (LiNiCoMnO₂); LFP—Lithium Iron Phosphate(LiFePO₄), LMO—Lithium Manganese Oxide (LiMn₂O₄); LCO—Lithium CobaltOxide (LiCoO₂); lithium oxides tor phosphates that contain nickel,cobalt or manganese, and LiTiS₂, LiNiO2, and other layered materials,other spinels, other olivines and tavorites, and combinations thereof.In an aspect, the electrochemically active cathode compounds can be anintercalation material or a cathode material that reacts with thelithium or other electrochemically active cathode material in a solidstate redox or conversion reaction. Such conversion cathode materialsinclude: metal halides including but not limited to metal fluorides suchas FeF₂, BiF₃, CuF₂, and NiF₂, and metal chlorides including but notlimited to FeCl₃, FeCl₂, CoCl₂, NiCl₂, CuCl₂, and AgCl; Sulfur (S);Selenium (Se); Tellerium (Te); Iodine (I); Oxygen (O); and relatedmaterials such as but not limited to pyrite (FeS₂) and Li₂S. As thesolid ionically conductive polymer electrolyte is stable at highvoltages (exceeding 5.0V relative the anode electrochemically activematerial), an aspect is to increase the energy density by enabling ashigh a voltage battery as possible, therefore high voltage cathodecompounds are preferred in this aspect. Certain NCM or NMC material canprovide such high voltages with high concentrations of the nickel atom.In an aspect, NCMs that have an atomic percentage of nickel which isgreater than that of cobalt or manganese, such as NCM_(7i2), NCM₇₂₁,NCM₈n, NCM₅₃₂, and NCM₅₂₃, are useful to provide a higher voltagerelative the anode electrochemically active material.

The cathode, like the anode, can be dispersed within the solid ionicallyconductive polymer material, by being mixed with it and an electricallyconductive material such as carbon or graphite. The cathode can beformed onto the bipolar current collector or formed as an independentstructure and place adjacent the bipolar current collector.

The aspects of the bipolar battery, its construction and its functionare described in the following examples

EXAMPLES

The battery article and its components are described here, and ways tomake and use them are illustrated in the following examples.

Example 1

PPS and chloranil powder are mixed in a 4.2:1 molar ratio (base polymermonomer to dopant ratio greater than 1:1). The mixture is then heated inargon or air at a temperature up to 350° C. for about twenty-four (24)hours at atmospheric pressure. A color change is observed confirming thecreation of charge transfer complexes in the polymer-dopant reactionmixture. The reaction mixture is then reground to a small averageparticle size between 1-40 micrometers. LiTFSI powder (12 wt. % of totalmixture) is then mixed with the reaction mixture to create thesynthesized solid, ionically conducting polymer material. The solid,ionically conducting polymer material which is used as a solid ionicallyconductive polymer electrolyte in this aspect is referred to as a solidpolymer electrolyte when thus used.

The solid ionically conductive polymer electrolyte can be used inmultiple locations in a battery, including in an electrode, or as astandalone dielectric, non-electrochemically active electrolyteinterposed between electrodes. When so used, the solid ionicallyconductive polymer electrolyte can be the same material in all batteryapplication, and in the aspect of a lithium battery if the ionicmobility of lithium is maximized, this property and attribute of thesolid ionically conductive polymer electrolyte allows the solidionically conductive polymer electrolyte to function well in an anode,cathode and as a standalone dielectric, non-electrochemically activeelectrolyte interposed between anode and cathode electrodes. However, inan aspect, the solid ionically conductive polymer electrolyte can varyso as to accommodate different properties that may be desired in anapplication. In a non-limiting example, an electronically conductivematerial could be added to the solid ionically conductive polymerelectrolyte or integrated into the solid ionically conductive polymerelectrolyte during its synthesis thus increasing the electricalconductivity of the solid ionically conductive polymer electrolyte andmaking it suitable for use in an electrode and reducing and oreliminating the need for additional electrical conductive additives insuch an electrode. If so used, such a formulation would not beappropriate for use as a standalone dielectric, non-electrochemicallyactive electrolyte interposed between anode and cathode electrodes as itis electrically conductive and would act to short the battery.

Further, use of the solid ionically conductive polymer electrolyte in ananode, cathode and as a standalone dielectric, non-electrochemicallyactive electrolyte interposed between anode and cathode electrodesenables a battery designer to take advantage of the thermoplastic natureof the solid ionically conductive polymer electrolyte. The standalonedielectric, non-electrochemically active electrolyte can be thermoformedonto the anode or cathode by being heated and fixed thereto, such as ina lamination process, or by being co-extruded and thus formed togetherwith the electrode. In an aspect all three battery components includethe solid ionically conductive polymer electrolyte and are thermoformedtogether or coextruded to form a battery.

Electronic conductivity of the synthesized material is measured usingpotentiostatic method between blocking electrodes, and was determined tobe 6.5×10″⁹ S/cm or lower (less conductive) than 1×10″⁸ S/cm.

Diffusivity measurements were conducted on the synthesized material.PGSE-MR measurements were made using a Varian-S Direct Drive 300 (7.1 T)spectrometer. Magic angle spinning technique was used to average outchemical shift anisotropy and dipolar interaction Pulsed gradient spinstimulated echo pulse sequence was used for the self-diffusion(diffusivity) measurements. The measurements of the self-diffusioncoefficients for the cation and anion in each material sample were madeusing 1H and ⁷Li nuclei, respectively. The material cation diffusivity D(⁷Li) of 0.23×10⁻⁹ m²/s at room temperature, and the anion diffusivity D(¹H) of was 0.45×10⁻⁹ m²/s at room temperature.

In order to determine the degree of ion association which would decreasethe conductivity of the material, the conductivity of the material iscalculated via the Nernst-Einstein equation, using the measureddiffusion measurements, it was determined the associated calculatedconductivity to be much greater than the measured conductivity. Thedifference was on average at least an order of magnitude (or 10×).Therefore, it is believed that conductivity can be improved by improvingion dissociation, and the calculated conductivities can be consideredwithin the range of conductivity.

The cation transference number can be estimated via equation (1) fromthe diffusion coefficient data as: t+˜D+/(D++D−) (1) where D+ and D−refer to the diffusion coefficients of the Li cation and TFSI anion,respectively. From the above data, one obtains a t+ value of about 0.7in the solid ionically conductive polymer material. This property ofhigh cation transference number has important implications to batteryperformance. Ideally one would prefer a t+ value of 1.0, meaning thatthe Li ions carry all the electric current. Anion mobility results inelectrode polarization effects which can limit battery performance. Thecalculated transference number of 0.7 is not believed to have beenobserved in any liquid or PEO based electrolyte. Although ionassociation may affect the calculation, electrochemical results confirmthe transference number range of between 0.65 and 0.75.

It is believed that the t+ is dependent on anion diffusion as lithiumcation diffusion is high. As the cation diffusion is greater than thecorresponding anion diffusion the cation transference number is alwaysabove 0.5, and as the anion is mobile the cation transference numbermust also be less than 1.0. It is believed that a survey of lithiumsalts as ionic compounds would produce this range of cation transferencenumbers greater than 0.5 and less than 1.0. As a comparative example,some ceramics have been reported to have high diffusion numbers, howeversuch ceramics only transport a single ion, therefore the cationtransference number reduces to 1.0 as the D− is zero.

Example 2

Additional solid ionically conductive polymer materials are listing inTable 3, along with the material synthesized and described in Example 1(PPS-Chloranil-LiTFSI), which were prepared using the synthesis methodof Example 1, along with their reactants and associated ionicconductivity (EIS method) at room temperature.

Ionic Polymer Conductivity (base) Dopant Ionic Compound (Wt %) (S/cm)PPS Chloranil LiTFSI (12) 6.0E−04 PPS Chloranil LiTFSI (4)  LiBOB(1)2.2E−04 PPS Chloranil LiTFSI (10) LiBOB(1) 7.3E−04 PPS Chloranil LiTFSI(10) LiBOB(1) 5.7E−04 PPS Chloranil LiFSI (10) LiBOB(1) 8.8E−04 PPSChloranil LiTFSI (5)  LiFSI (5)  LiBOB(1) 1.3E−03

Various physical properties of the solid ionically conductive polymermaterials are measured and it is determined that the solid ionicallyconductive polymer materials: electronic conductivity of the solidionically conductive polymer material is less than 1×10″⁸ S/cm at roomtemperature; can be molded to thicknesses from 200 micrometers down to20 micrometers; possesses significant ionic mobility to very lowtemperatures. e.g. −40° C., and have ionic conductivities at roomtemperature greater than 1.0E-05 S/cm, 1.0E−04 S/cm, and 1.0E−03 S/cm,and these ionic conductivities include lithium as one of the mobile ionsbeing conducted through the solid ionically conductive polymer material.

Example 3

The solid ionically conductive polymer electrolyte of Example 2,specifically PPS/Chloranil/LiTFSI—LiFSI—LiBOB, was used to make abipolar secondary lithium cell. The cell comprised a lithium metalanode, the solid ionically conductive polymer electrolyte was used as anelectrolyte layer and interposed between the anode and a slurry cathode.The slurry cathode also comprised the solid ionically conductive polymerelectrolyte and the cathode is manufactured using a stepwise process.The process initially includes a polyvinylidene difluoride (PVDF) binderin a solvent such as N-Methyl-2-pyrrolidone (MP) or Dimethylacetamide(DMA). Electrically conductive carbon and graphite and the solidionically conductive polymer electrolyte are then added in a firstmixing step in which the carbon and solid ionically conductive polymerelectrolyte remain stable and insoluble in the binder solvent. Thisfirst mixture is then mixed in a second mixing step with aelectrochemically active cathode material such as Lithium cobalt oxide(LiCoO₂) (“LCO”) to create a slurry mix which is then coated onto acathode collector. After a drying step in which the binder solvent isdriven out of the cathode, the cathode is calendared to create a highdensity cathode.

Table 4 details composition ranges for each of the cathode componentsincluded in the described slurry cathode process.

TABLE 4 Cathode Component Wt. % Electrochemically Active Material 70-90Solid ionically conductive polymer  4-15 electrolyte Electricallyconductive carbon 1-5 Electrically conductive graphite 1-5 Binder 3-5

The high density cathode is about 15 to 115 micrometers in thickness,and has a cathode coating density in the range of 1.2 to 3.6 g/cc.

Example 4

Bipolar batteries were assembled using Li metal anodes. Cathodes wereprepared incorporating electrochemically active material listed in Table5, and according to the method described in Example 3, and the lithiummetal anode is positioned opposite the cathode on the current collectorto create a bipolar electrode including the solid ionically conductivepolymer material. A film of the solid ionically conductive polymermaterial is located between the anodes and cathodes layers or betweenthe bipolar electrodes. Three layers of bipolar electrodes were used inthe battery giving a total cell voltage of listed in Table 5. Since thesolid ionically conductive polymer material was used in this battery, noattempt was made to seal between the bipolar electrodes; and all of thelayers were stacked directly adjacent each other. This is in contrast toa liquid electrolyte system, where great care and elaborate cell designis needed to ensure that the liquid electrolyte is sealed and does notcross over from one bipolar electrode to another. Conductive tabs areaffixed to the terminal cathode and anode layers.

After assembling the bipolar battery using the described electrodes andsolid ionically conductive polymer material, the battery was vacuumsealed in aluminum laminate pouch material in a manner so the conductivetabs protrude from the pouch to act as terminal leads for the bipolarpouch cell.

TABLE 5 Cathode No. of Initial Cell Anode Material Material Cathodes OCV(V) 160217-9-5  Lithium Metal NCM 2 6.80 160219-11-3 Lithium Metal NCM 310.22 160226-13-1 Lithium Metal LCO 3 9.65 160228-16-1 Lithium Metal LCO3 9.44 160325-22-4 Lithium Metal LCO 3 9.75

Example 5

The bipolar pouch cells (batteries) from Example 4 are tested todetermine voltage stability, performance, cycling efficiency and shelflife. Referring to FIG. 2A and FIG. 2B, a bipolar pouch cells comprisinga NCM cathode was tested for stability. FIG. 2A is a charge curve whichdisplays stable voltage for the first cycle of the cell. FIG. 2B showsthe high rate pulse discharge of this same bipolar cell, anddemonstrates the bipolar cell is able to handle current density as highas 3.0 mA/cm2, well above the minimum voltage of the battery. The Limetal/solid ionically conductive polymer material/NCM bipolar cell waspulse discharge tested for 5 sec pulse lengths at currents of 5, 20, 40,80 and 120 mA. These currents correspond to 0.125, 0.5, 1.0, 2.0, and3.0 mA/cm2 current density, respectively. All of the currents utilizedhere were readily handled by the cell, with the minimum voltagesignificantly above the 9 V minimum voltage for the cell.

Example 6

The bipolar pouch cells (batteries) from Example 4 were additionallytested to determine voltage stability, performance, cycling efficiencyand shelf life Specifically, one of the bipolar pouch cells comprising aLCO cathode was cycled with a nine (9) hour rest after charge. Referringto FIG. 3 , the charge voltage exceeds 12 volts on the first cycle, andwhich is repeated in the second cycle. The nine (9) hour rest time afterthe initial charge demonstrates the voltage stability of the cell, sincethe open circuit storage voltage remains stable, and above 12 V duringthis time period.

Referring to FIG. 4 a longer discharge curve is shown which displays theentire second cycle. From the first two charge-discharge cycles a cyclicefficiency can be calculated using coulombs required for the charge, andcoulombs derived during discharge. The coulombic measurements can benormalized relative to the weight of the electrochemically activecathode material for a mAh/gram capacity measurement. The dischargevalue is divided by the charge value for a cycle and multiplied by 100to yield a n-cycle efficiency. The first cycle charge capacity wascalculated to be 162.8 mAh/g, with the associated discharge capacity146.3 mAh/g. In the second cycle, the first cycle charge capacity wascalculated to be 149.1 mAh/g, with the associated discharge capacity148.6 mAh/g for a second cycle cyclic efficiency of over 99%.

Referring to FIG. 5 , there is shown an open circuit voltage plot of thesame bipolar pouch cell over many days. To the extent there wasshorting, bridging or other interaction between the electrodes the OCVwould show a change. However, the bipolar cell is stable over a manyweek time period.

Example 7

A bipolar battery was assembled using Li metal anodes, and sulfurcathodes incorporating sulfur electrochemically active material and thesolid ionically conductive polymer material from Example 1, with anelectrically conductive copper collector positioned there between toform a bipolar electrode. A film of the solid ionically conductivepolymer material between the bipolar electrodes and interposed betweenadjacent anodes and cathodes. Three layers of anode/solid ionicallyconductive polymer material/cathode were used in the battery giving atotal cell voltage of approximately 7.0 V (each sub-stack contributing˜2.33 V to the total bipolar battery voltage). Since the solid ionicallyconductive polymer material was used in this battery, no attempt wasmade to seal between the bipolar layers; all of the layers were stackeddirectly on top/adjacent of each other. This is in contrast to a liquidelectrolyte system, where great care and elaborate cell design is neededto ensure that the liquid electrolyte is sealed and does not cross overfrom one bipolar cell stack to another, shorting the battery.

After assembling the bipolar battery using the described electrodes andpolymer electrolyte, the battery was vacuum sealed in aluminum laminatepouch material. The open circuit voltage of the bipolar battery wasmonitored over several months to determine the stability of the cell. Astable cell chemistry would be expected to have an open circuit voltagethat is stable over time. The results are presented in FIG. 6 , whichshow OCV stability at the predicted 7.0 Volts for over one half year.

During a four-month storage of the bipolar Li/Sulfur cell, the impedancechange was very slight, and varied over time, most likely due to slightchanges in room temperature during the impedance measurement. Referringto FIG. 7 which includes the initial impedance and the 4-month storageimpedance, which are virtually identical, the cell does not change inimpedance over several months of storage—thus the cell has very stablecomponents.

These data are indicative of a stable electrochemical system and showsthat the use of this applications polymer electrolyte in the cathode andas the solid ionically conductive polymer material for this bipolarsystem provides a stable battery. One skilled in the art can see thatthis invention leads to great flexibility in the practical applicationof these bipolar batteries. The number of bipolar cell layers can bevaried to produce the desired output voltage to meet the needs of theparticular device. Thus, high output voltages can be delivered by asingle, compact and energy dense bipolar battery.

Example 8

Additional bipolar batteries were assembled using two or three bipolarcell stacks. These bipolar batteries were constructed using MnO₂cathodes (MnO2 mixed with the solid ionically conductive polymermaterial, and an electrically conductive graphite or similar material)and Aluminum anodes, both containing the solid ionically conductivepolymer material. The solid ionically conductive polymer material wasprepared according to Example 1, however the ionic compound used waslithium hydroxide monohydride. Alkaline liquid electrolyte (potassiumhydroxide solution) was used and properly sealed in these cells. No cellshorting or electrolyte leakage was observed. These cells havedemonstrated capabilities to power electronic devices such as iPod Nano,LED lights, etc. While the invention has been described in detail hereinin accordance with certain aspects thereof, many modifications andchanges therein may be affected by those skilled in the art withoutdeparting from the spirit of the invention.

Accordingly, it is our intent to be limited only by the scope of theappending claims and not by way of the details and instrumentalitiesdescribing the embodiments shown herein.

It is to be understood that variations and modifications can be made onthe aforementioned structure without departing from the concepts of thepresent invention, and further it is to be understood that such conceptsare intended to be covered by the following claims unless these claimsby their language expressly state otherwise.

What is claimed is:
 1. A battery comprising: a positive electrodecomprising a first electrochemically active material; a negativeelectrode comprising a second electrochemically active material; and oneor more electrolyte layers, wherein each of the one or more electrolytelayers each comprise a solid ionically conductive polymer materialcomprising a polymer, a dopant, and an ionic compound, and wherein thesolid ionically conductive polymer material comprises at least onecationic diffusing ion and at least one anionic diffusing ion.
 2. Thebattery of claim 1, wherein the at least one cationic diffusing ionand/or the at least one anionic diffusing ion is mobile in the glassystate.
 3. The battery of claim 1, wherein the positive electrode and thenegative electrode each comprise a sub-stack which also includes anelectrolyte layer, wherein each sub-stack is separated from an adjacentsub-stack by an electrically conductive sheet, wherein each sub-stackhas a voltage, and the voltage of each sub-stack is equal to or lessthan 3 volts.
 4. The battery of claim 3 further comprising a secondsub-stack comprising a second separator layer comprising a solidionically conductive polymer electrolyte positioned between a secondanode layer and second cathode layer, wherein said second sub-stack ispositioned adjacent to and in electrical but not in ionic communicationwith the first sub-stack and further comprising a current collectorlayer positioned adjacent to the second sub-stack.
 5. The battery ofclaim 1, wherein the first electrochemically active material compriseszinc, aluminum, lithium, an intercalation material, a lithium oxidecomprising nickel, cobalt or manganese, lithium nickel cobalt aluminumoxide; lithium nickel cobalt manganese oxide, lithium iron phosphate,lithium manganese oxide; lithium cobalt phosphate or lithium manganesenickel oxide, lithium cobalt oxide, LiTiS₂, LiNiO2, or combinationsthereof.
 6. The battery of claim 1, wherein the second electrochemicallyactive material comprises manganese dioxide, sulfur, an intercalationmaterial, or combinations thereof.
 7. The battery of claim 1 wherein thepositive electrode comprises the solid ionically conductive polymermaterial.
 8. The battery of claim 1 wherein the negative electrodecomprises the solid ionically conductive polymer material.
 9. Thebattery of claim 1, wherein the solid ionically conductive polymermaterial has a crystallinity greater than 30%.
 10. The battery of claim1, wherein the solid ionically conductive polymer material furthercomprises a plurality of charge transfer complexes.
 11. The battery ofclaim 10, wherein the solid ionically conductive polymer materialcomprises a plurality of monomers, and wherein each charge transfercomplex is positioned on a monomer.
 12. The bipolar battery of claim 1,wherein the electronic conductivity of the solid ionically conductivepolymer material is less than 1×10⁻⁸ S/cm at room temperature.
 13. Thebattery of claim 1, wherein the ionic conductivity of solid ionicallyconductive polymer material is greater than 1.0×10⁻⁵ S/cm at roomtemperature.
 14. The battery of claim 1, wherein the melting temperatureof the solid ionically conductive polymer material is greater than 250°C.
 15. The battery of claim 1, wherein the solid ionically conductivepolymer material is a thermoplastic.
 16. The battery of claim 1, whereina cationic transference number of the solid ionically conductive polymermaterial is greater than 0.5 and less than 1.0.
 17. The battery of claim1, wherein at least one anionic diffusing ion comprises hydroxide,fluorine or boron.
 18. The battery of claim 1, wherein the solidionically conductive polymer material comprises a plurality of monomers,wherein each monomer comprises an aromatic or heterocyclic ringstructure positioned in the backbone of the monomer and the solidionically conductive polymer material further includes a heteroatomincorporated in the ring structure or positioned on the backboneadjacent the ring structure.
 19. The battery of claim 1, wherein atleast one of the one or more electrolyte layers is in the form of a filmhaving a thickness of between 200 and 10 micrometers.
 20. The battery ofclaim 1, wherein the dopant is selected from the group consisting of:quinones, 2,3-dicyano-5,6-dichlorodicyanoquinone (CsCl₂N₂O₂),tetrachloro-1,4-benzoquinone (C₆Cl₄O₂), tetracyanoethylene (C₆N₄),sulfur trioxide (SO₃), ozone (O₃), oxygen (O₂), air, transition metals,manganese dioxide (MnO₂), an electron acceptor, and combinationsthereof.